EP2119737B1 - Electronic packaging - Google Patents
Electronic packaging Download PDFInfo
- Publication number
- EP2119737B1 EP2119737B1 EP08156292A EP08156292A EP2119737B1 EP 2119737 B1 EP2119737 B1 EP 2119737B1 EP 08156292 A EP08156292 A EP 08156292A EP 08156292 A EP08156292 A EP 08156292A EP 2119737 B1 EP2119737 B1 EP 2119737B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- epoxy
- resin composition
- epoxy resin
- dihydroxy
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 0 CC*(*)C(CCC=IC)=CN(C)C Chemical compound CC*(*)C(CCC=IC)=CN(C)C 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
Definitions
- the present invention relates to an epoxy resin composition which is useful for encapsulating electric and electronic materials, particularly electric parts such as an adhesive, paint, insulation material and laminate.
- the epoxy resin encapsulant is required to have low moisture absorption, high crack resistance and improved adhesion. Further, for obtaining low moisture absorption, an epoxy resin of low viscosity in which a filler can be filled in high concentration is desired.
- an encapsulating material in which glycidyl ether of o-cresol novolak is used as a polyfunctional epoxy resin and phenol novolak is used as a curing agent is mainly used, however, when the encapsulating material absorbs moisture in storage, the above-described problems occur. Therefore, for avoiding these problems, the encapsulating material is wrapped for preventing moisture absorption in practical use.
- a biphenyl type epoxy resin in current use has a lower viscosity and can contain a filler in higher concentration than a polyfunctional epoxy resin, since the biphenyl epoxy resin is a bifunctional epoxy resin and has a low molecular weight. Therefore, moisture absorption depending on the biphenyl type epoxy resin can be reduced as whole package and strength thereof can be increased, consequently, excellent crack resistance can be obtained as compared with an epoxy resin in the form of a glycidyl ether of o-cresol novolak.
- the biphenyl type epoxy resin has problem that molding property of a cured article thereof is low as compared with the polyfunctional epoxy resin.
- a dicyclopentadiene type epoxy resin which has curing ability between that of the biphenyl type epoxy resin and that of the cresol novolak type epoxy resin is commercially available.
- the dicyclopentadiene type epoxy resin has a low melting point and tends to adhere each other, therefore, the resin should be cooled and preserved, consequently, there is also a problem in handling a large amount of the resin as above.
- the dicyclopentadiene type epoxy resin contains a small number of epoxy groups per unit weight of resin, therefore curing and molding property thereof are sometimes insufficient, and further, heat resistance of the cured and molded article are also sometimes insufficient, since the resin has an alicyclic structure derived from non-reactive dicyclopentadiene.
- the biphenyl type bifunctional epoxy resin has a problem that curing and molding property is poor since the number of epoxy functional group is small per one molecule, unlike the cresol novolak type polyfunctional epoxy resin. Specifically, Barcole hardness of the biphenyl type resin slightly lowers in molding as compared with the polyfunctional epoxy resin, therefore, a method for enhancing Barcole hardness has been desired.
- An object of the present invention is to provide a resin composition which is an excellent material as an epoxy semiconductor encapsulating material, obtained by using an epoxy resin which has excellent molding property and excellent handling property even at room temperature, and a resin encapsulated semiconductor device using the resin composition.
- the present invention is an epoxy resin composition comprising:
- the present invention relates to a resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the above epoxy resin composition.
- substituents R1 to R9 of the epoxy resin represented by the general formula (1) used in the present invention include methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group (including respective isomers), chlorine atom , bromine atom and the like.
- the epoxy resin represented by the general formula (I) can be obtained by glycidyl-etherifying stilbenephenols according to a conventional method.
- a literature discloses a production method of a stilbene-based bisphenol compound which is a raw material of the epoxy resin, and physical properties of compounds such as 4,4'-dihydroxystilbene, 4,4'-dihydroxy-3,3'-dimethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethylstilbene and the like.
- Another literature METHODEN DER ORGANISCHEN CHEMIE (HOUBEN-WEYL) BAND IV/1c Phenol Mol Mol 2 P1034 ) describes a production method of 4,4'-dihydroxy- alpha -methylstilbene, etc. using phenol and chloroacetone as a starting material.
- stilbene-based phenols used as a raw material of the epoxy resin represented by the general formula (1) include 4,4'-dihydroxy-3-methylstilbene, 4,4'-dihydroxy-3-ethylstilbene, 4,4'-dihydroxy-3-propylstilbene, 4,4'-dihydroxy-3-amylstilbene, 4,4'-dihydroxy-3-hexylstilbene, 4,4'-dihydroxy-2,3-dimethylstilbene, 4,4'-dihydroxy-2,6-dimethylstilbene, 4,4'-dihydroxy-2,3'-dimethylstilbene, 4,4'-dihydroxy-3,3',5-trimethylstilbene, 4,4'-dihydroxy-3,3',5-trimethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethylstilbene, 4,4'-dihydroxy-2',3,5,6'-tetramethylstilbene, 3-t-butyl-4,4'-dihydroxy-3'-
- Epoxy compounds of alpha -methylstilbene obtained by substituting a carbon atom on a carbon-carbon double bond of these stilbene compounds with a methyl group are also exemplified.
- epoxy resins are obtained by reacting bisphenols with an epihalohydrin in the presence of an alkaline such as sodium hydroxide and the like. Particularly, when an epoxy resin having high purity is obtained, a reaction in the presence of an aprotic solvent is suitable as described in Japanese Patent Application Laid-Open (JP-A) No. 60-31,517 .
- polyfunctional epoxy compound (B) having a functional group number of two or more there can be used known compounds, and examples thereof include novolak-based epoxy resins which are reaction products of formaldehyde with phenols such as phenol, o-cresol and the like; glycidyl ether compounds derived from three or more-functional phenols such as phloroglycine, tris-(4-hydroxyphenyl)-methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane and the like; glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds; amine-based epoxy resins derived from p-aminophenol, m-aminophenol, 4-aminomethacresol, 6-aminomethacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,
- the resin composition of the present invention may contain glycidyl ester-based compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid and the like, such as bisphenol A, bisphenol F, tetramethylbiphenol, hydroquinone, resorcin, 4,4'-thiodi(2,6-dimethylphenol), dihydroxynaphthalene, bis(hydroxyphenyl)dicyclopentane, bis(hydroxyphenyl)menthane and the like; hydantoin-based epoxy compounds derived from 5,5-dimethylhydantoin and the like; alicyclic epoxy resins such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexenedioxide, 3,4-epoxycyclohe
- the epoxy resin component of the present invention is obtained by mixing the stilbene-based epoxy compound (A) represented by the general formula (1) with the polyfunctional epoxy compound (B).
- the content of the epoxy compound (A) is, for example, from 1 to 99% by weight, preferably from 20 to 99% by weight, and more preferably from 30 to 90% by weight based on the total amount of the epoxy compound (A) and the epoxy compound (B).
- the content of the epoxy compound(A) is, for example, from 1 to 60% by weight based on the total amount of the epoxy compound (A) and the epoxy compound(B), flowing property of the whole composition is improved and a molded article having high Barcole harness can be obtained.
- the content of the epoxy compound(A) is preferably from 20 to 60% by weight, and more preferably from 30 to 60% by weight which are epoxy resin components. When the content is lower than 1% by weight, the softening point becomes lower to make the handling property insufficient.
- the epoxy compound (A) has a low melt viscosity and can contain a large amount of filler without deteriorating flowing property of the whole resin composition, but the epoxy compound (A) alone, sometimes cannot afford a molded article having high Barcole hardness.
- the polyfunctional epoxy compound (B) with the stilbene-based epoxy compound (A), it becommes possible to increase crosslinking density to make the Barclole hardness high.
- the content of the polyfunctional epoxy compound (B) is, for example, from 1 to not more than 40% by weight based on the total amount of the epoxy compound(A) and the epoxy compound(B), preferably from 1 to 30% by weight, and more preferably from 10 to 30% by weight.
- the content is lower than 1% by weight, the effect of improving Barcole hardness is insufficient.
- the epoxy compound (A) of the present invention has a melt viscosity at 150 DEG C of preferably less than 1 poise, and more preferably less than 0.5 poise.
- the polyfunctional epoxy compound (B) has a melt viscosity at 150 DEG C of preferably less than 10 poise, and more preferably less than 5 poise.
- the epoxy compound (A) and the polyfunctional epoxy resin (B) may be mixed with a filler and the like, or the epoxy components may be previously melted and mixed or may be melted and mixed previously with the resin component (C) such as an epoxy curing agent and the like before use.
- epoxy curing agent (C) known curing agents can be used. Examples thereof include polyhydric phenols such as phenol novolak and the like, amine-based curing agents such as dicyanediamide, diaminodiphenylmethane, diaminodiphenylsulfone and the like, acid anhydride curing agents such as pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid, and the like, and in view of moisture resistance, polyhydric phenols are preferable.Further, examples of polyhydric phenols as the epoxy curing agent include polycondensates of one or more phenols such as phenol, various alkylphenols, naphthol and the like with aldehydes such as formaldehyde, acetaldehyde, acrolein, glyoxal, benzaldehyde, naphthaldehyde, hydroxybenzaldehyde and the like or
- the amount of the curing agent is preferably from 0.7 to 1.2 equivalent based on the epoxy resin.
- the amount is less than 0.7 equivalent, or more than 1.2 equivalent, curing is incomplete in either case.
- accelerators include, but not limited to, organic phosphine compounds such as triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cycnoethylphosphine and the like and tetraphenyl borate salts thereof; tert-amines such as tributylamine, triethylamine, 1,8-diazabicyclo(5,4,0)undecene-7, triamylamine and the like; quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammoniumtetraphenyl borate and the like; imidazoles, and the like.
- organic phosphine compounds 1,8-diazabicyclo(5,4,0)undec
- Examples of the inorganic filler (D) in the epoxy resin composition of the present invention include silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass, fiber and the like, and in particular, silica and alumima are preferred. These fillers having different form (spherical or crushed type) or different size may also be mixed to increase filling amount for use.
- the compounding ratio of the inorganic filler is from 25 to 95% by weight based on the total amount of the resin composition, preferably from 50 to 95% by weight, more preferably from 70 to 95% by weight, and more preferably from 80 to 92% by weight.
- the form may advantageously be substantial sphere containing no sharp angle and having an aspect ratio of 1.0 to 1.2.
- a sphere having sphericity near that of a commercially available spherical silica powder produced by a spray coating method or sol-gel method is preferred, and a sphere having sphericity more close to that of a real sphere is more preferable.
- the inorganic material is processed into a fine powder, and then formed to a spherical powder by a mechanochamichal method with adding a binder to the powder.
- the form of the crushed powder may be heteromorphic body such as a polyhedron having angle and the like.
- amorphous or crystalline quarts crushed powders obtained by grinding a synthetic or natural quarts lump is suitable, and specifically, fused crushed-silica and the like are suitable.
- any powder can be used, and as one example, which composed of three groups, namely, x, y and z components, will be described.
- the x, y and z components have an average particle size from 0.1 to 1.5 mu m, an average particle size from 2 to 15 mu m and an average particle size from 20 to 70 mu m respectively, and more preferably an average particle size from 0.1 to 1.0 mu m, an average particle size from 2 to 10 mu m and an average particle size from 20 to 50 mu m respectively.
- the powder having an average particle size of less than 0.1 mu m When a powder having an average particle size of less than 0.1 mu m is used, due to flocculation of the powder each other, sometimes uniform dispersion in the resin composition becomes difficult and flowing property is lost, and the powder having an average particle size of over 70 mu m can not easily filled in fine part of a semiconductor element.
- flowing property of the resin composition lowers.
- the particle size distribution of each spherical powder used in the present invention is narrower, and further, a powder of monodistribution system is preferred. Therefore, it is preferable to use a powder in which x, y and z components are treated for uniforming respective particle sizes by sieving operation.
- the average particle size is defined as a 50 % diameter of cumulative particle distribution measured by using an apparatus such as a laser scattering particle size distribution measuring apparatus and the like.
- ratios by volume of the x, y and z components based on the calculated total volume of the x, y and z components may be advantageously from 10 to 24% by volume, from 0.1 to 66% by volume and from 24 to 76% by volume respectively, and more advantageously from 10 to 24% by volume, from 0.1 to 36% by volume and from 57 to 76% by volume respectively, and more preferably from 10 to 20% by volume, from 4 to 30% by volume and from 60 to 76% by volume respectively.
- flowing property of the resin composition lowers.
- % by weight in the present invention are obtained by calculation using values obtained by dividing respective weights of the w, y and z components by respective true specific gravity, as volumes of respective components.
- apparent volume of a particle having particle size distribution changes depending on manner for filling into a measuring vessel, and when aggregates of heterogeneous particles are mixed, the apparent volumes before and after the mixing are different. Therefore, in the above-described description, apparent volume is not used in calculation of % by volume of each component of the particle aggregate.
- the crushed powder (m component) used in the present invention has an average particle size of 1 to 70 mu m, preferably 1 to 30 mu m.
- the ratio by weight of them component based on the total weight of the spherical powder component and the crushed powder m component is preferably from 1 to 30% by weight.
- the epoxy resin composition according to the invention contains a pyrogenically produced silica, which has been surface modified with Hexamethyldisilazane (HMDS) and structurally modified by a ball mill.
- HMDS Hexamethyldisilazane
- This pyrogenically produced silica is known from the US 5,959,005 .
- the pyrogenically produced, hydrophobized and structurally modified silica can be the AEROSIL R8200, which has the following physical-chemical datas: Properties Unit Typical Value Specific surface area (BET) m 2 /g 160 ⁇ 25 Carbon content wt. % 2.0 - 4.0 Tapped density* (approx. value) acc. to DIN EN ISO 787/11, Aug. 1983 g/l approx. 140 Moisture* 2 hours at 105 °C wt. % ⁇ 0.5 pH-value in 4 % dispersion ⁇ 5.0 SiO 2 -content based on ignited material wt. % ⁇ 99.8 * ex plant
- the data represents typical values and not production parameters Registration CAS-No.
- the fillers used in the present invention is previously mixed sufficiently.
- the mixing can be conducted by using an apparatus such as a mixer, cokneader and the like utilizing a rotating blade or air, an apparatus which vibrates, shakes or rotates a vessel, and the like.
- an apparatus such as a mixer, cokneader and the like utilizing a rotating blade or air, an apparatus which vibrates, shakes or rotates a vessel, and the like.
- the filler may be previously treated with a coupling agent or a resin, for use.
- the treatment method there are a method in which mixing is conducted using a solvent, then the solvent is distilled off, and a method in which the coupling agent or the resin is directly mixed with the filler, and the mixture is treated using a mixed.
- a mold-releasing agent such as natural wax, synthetic wax, higher fatty acid and metal salt thereof, or paraffin and the like, or a coloring agent such as carbon black, and further, a surface treating agent such as a silane coupling agent and the like, may be optionally added.
- a flame retardant such as antimony trioxide, phosphorus compound, brominated epoxy resin and the like may be added. For exhibiting flame retardant effect, a brominated epoxy resin is particularly preferable.
- various elastomers may be added or previously reacted for use.
- elastomers include addition type or reaction type elastomers and the like such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber, silicone oil and the like.
- curing-molding may advantageously be effected by a conventionally known molding method such as transfer mold, compression mold, injection mold and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Control And Other Processes For Unpacking Of Materials (AREA)
- Glass Compositions (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
- The present invention relates to an epoxy resin composition which is useful for encapsulating electric and electronic materials, particularly electric parts such as an adhesive, paint, insulation material and laminate.
- Recently, for encapsulating semiconductors such as LSI, IC, transistor and the like, transfer mold of an economically useful epoxy resin composition is conducted.
- Particularly, surface amounting of LSI is recently conducted, and direct immersion into a solder bath is increasing. Since an encapsulating material is exposed to high temperature in this treatment, moisture absorbed in the encapsulating material expands, crack is formed in the material, and peeling occurs at interface with a die pat.
- Therefore, the epoxy resin encapsulant is required to have low moisture absorption, high crack resistance and improved adhesion. Further, for obtaining low moisture absorption, an epoxy resin of low viscosity in which a filler can be filled in high concentration is desired. Currently condition, an encapsulating material in which glycidyl ether of o-cresol novolak is used as a polyfunctional epoxy resin and phenol novolak is used as a curing agent is mainly used, however, when the encapsulating material absorbs moisture in storage, the above-described problems occur. Therefore, for avoiding these problems, the encapsulating material is wrapped for preventing moisture absorption in practical use.
- On the other hand, a biphenyl type epoxy resin in current use has a lower viscosity and can contain a filler in higher concentration than a polyfunctional epoxy resin, since the biphenyl epoxy resin is a bifunctional epoxy resin and has a low molecular weight. Therefore, moisture absorption depending on the biphenyl type epoxy resin can be reduced as whole package and strength thereof can be increased, consequently, excellent crack resistance can be obtained as compared with an epoxy resin in the form of a glycidyl ether of o-cresol novolak. However, the biphenyl type epoxy resin has problem that molding property of a cured article thereof is low as compared with the polyfunctional epoxy resin.
- There is also a method in which molding property is improved by combining the current biphenyl type epoxy resin with the cresol novolak type epoxy resin with maintaining the resin viscosity at suitable level, however, the mixture of the biphenyl type epoxy resin and the cresol novolak type epoxy resin becomes semisolid state (honey-like state) and has no definite shape after melt mixing, therefore, handling property of the resin is insufficient. Further, the mixed resin tends to adhere each other, therefore, there is a problem in handling a large amount of the resin.
- On the other hand, a dicyclopentadiene type epoxy resin which has curing ability between that of the biphenyl type epoxy resin and that of the cresol novolak type epoxy resin is commercially available. There is a problem that the dicyclopentadiene type epoxy resin has a low melting point and tends to adhere each other, therefore, the resin should be cooled and preserved, consequently, there is also a problem in handling a large amount of the resin as above.
- In addition, the dicyclopentadiene type epoxy resin contains a small number of epoxy groups per unit weight of resin, therefore curing and molding property thereof are sometimes insufficient, and further, heat resistance of the cured and molded article are also sometimes insufficient, since the resin has an alicyclic structure derived from non-reactive dicyclopentadiene.
- The biphenyl type bifunctional epoxy resin has a problem that curing and molding property is poor since the number of epoxy functional group is small per one molecule, unlike the cresol novolak type polyfunctional epoxy resin. Specifically, Barcole hardness of the biphenyl type resin slightly lowers in molding as compared with the polyfunctional epoxy resin, therefore, a method for enhancing Barcole hardness has been desired.
- An object of the present invention is to provide a resin composition which is an excellent material as an epoxy semiconductor encapsulating material, obtained by using an epoxy resin which has excellent molding property and excellent handling property even at room temperature, and a resin encapsulated semiconductor device using the resin composition.
- That is, the present invention is an epoxy resin composition comprising:
- (A) an epoxy compound represented by the general formula (1):
- (B) a polyfunctional epoxy compound having a functional group number of two or more, and
- (C) an epoxy curing agent containing a phenolic hydroxyl group,
wherein the proportion of the epoxy compound (A) is from 1 to 99% by weight based on the total weight of the epoxy compounds (A) and (B), whereas the epoxy resin composition contains a pyrogenically produced silica, which has been surface modified with Hexamethyldisilazane (HMDS) and structurally modified by a ball mill. - Further, the present invention relates to a resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the above epoxy resin composition.
- Specific examples of the respective substituents R1 to R9 of the epoxy resin represented by the general formula (1) used in the present invention include methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group (including respective isomers), chlorine atom , bromine atom and the like.
- The epoxy resin represented by the general formula (I) can be obtained by glycidyl-etherifying stilbenephenols according to a conventional method.
- A literature (von Rolf H. Sieber, Liebigs Ann. Chem. 730, 31 to 46 (1969)) discloses a production method of a stilbene-based bisphenol compound which is a raw material of the epoxy resin, and physical properties of compounds such as 4,4'-dihydroxystilbene, 4,4'-dihydroxy-3,3'-dimethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethylstilbene and the like. Another literature (METHODEN DER ORGANISCHEN CHEMIE (HOUBEN-WEYL) BAND IV/1c Phenol Teil 2 P1034) describes a production method of 4,4'-dihydroxy- alpha -methylstilbene, etc. using phenol and chloroacetone as a starting material.
- Specific examples of the stilbene-based phenols used as a raw material of the epoxy resin represented by the general formula (1) include 4,4'-dihydroxy-3-methylstilbene, 4,4'-dihydroxy-3-ethylstilbene, 4,4'-dihydroxy-3-propylstilbene, 4,4'-dihydroxy-3-amylstilbene, 4,4'-dihydroxy-3-hexylstilbene, 4,4'-dihydroxy-2,3-dimethylstilbene, 4,4'-dihydroxy-2,6-dimethylstilbene, 4,4'-dihydroxy-2,3'-dimethylstilbene, 4,4'-dihydroxy-3,3',5-trimethylstilbene, 4,4'-dihydroxy-3,3',5-trimethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethylstilbene, 4,4'-dihydroxy-2',3,5,6'-tetramethylstilbene, 3-t-butyl-4,4'-dihydroxy-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-5,3'-dimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3',6-dimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3'-methyl-5-propylstilbene, 3-t-butyl-4,4'-dihydroxy-5-butyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-5-amyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-5-hexyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-5-cyclohexyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-3,5,5'-trimethylstilbene, 3-t-butyl-2,4'-dihydroxy-3',5',6-trimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3',5',6-trimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3',5-dimethyl-5'-propylstilbene, 3-t-butyl-4,4'-dihydroxy-3',6-dimethyl-5'-propylstilbene, 4,4'-dihydroxy-3,3'-dimethylstilbene, 3,3'-diethyl-4,4'-dihydroxystilbene, 4,4'-dihydroxy-3,3'-dipropylstilbene, 3,3'-diamyl-4,4'-dihydroxystilbene, 3,3'-dihexyl-4,4'-dihydroxystilbene, 3,3'-dicyclohexyl-4,4'-dihydroxystilbene, 2,2'-dihydroxy-3,3',5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,2'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetra-t-butylstilbene and the like (including isomers having different substitution position). Epoxy compounds of alpha -methylstilbene obtained by substituting a carbon atom on a carbon-carbon double bond of these stilbene compounds with a methyl group are also exemplified. Among these compounds, 2,2'-dihydroxy-3,3',5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3',5,5'-tetramethyl- alpha -methylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,2'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3',5,5'-trimethylstilbene, 3-t-butyl-2,4'-dihydroxy-3',5',6-trimethylstilbene and 3-t-butyl-4,4'-dihydroxy-3',5',6-trimethylstilbene are particularly preferable from the viewpoints of easiness of synthesis, performances, and price of the raw material.
- These epoxy resins are obtained by reacting bisphenols with an epihalohydrin in the presence of an alkaline such as sodium hydroxide and the like. Particularly, when an epoxy resin having high purity is obtained, a reaction in the presence of an aprotic solvent is suitable as described in Japanese Patent Application Laid-Open (JP-A) No.
60-31,517 - In the epoxy resin composition of the present invention, as polyfunctional epoxy compound (B) having a functional group number of two or more, there can be used known compounds, and examples thereof include novolak-based epoxy resins which are reaction products of formaldehyde with phenols such as phenol, o-cresol and the like; glycidyl ether compounds derived from three or more-functional phenols such as phloroglycine, tris-(4-hydroxyphenyl)-methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane and the like; glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds; amine-based epoxy resins derived from p-aminophenol, m-aminophenol, 4-aminomethacresol, 6-aminomethacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis-(methylamine) and the like, and one or more of these epoxy resins are used.Among them, novolak-based epoxy resins which are reaction products of folmaldehyde with phenols such as phenol, o-cresol and the like, and glycidyl ether compounds of polyhydric phenols containing a trismethane group obtained by condensation reaction of phenols with aromatic carbonyl compounds are particularly preferable in view of heat resistance, easy availability and cost.
- The resin composition of the present invention may contain glycidyl ester-based compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid and the like, such as bisphenol A, bisphenol F, tetramethylbiphenol, hydroquinone, resorcin, 4,4'-thiodi(2,6-dimethylphenol), dihydroxynaphthalene, bis(hydroxyphenyl)dicyclopentane, bis(hydroxyphenyl)menthane and the like; hydantoin-based epoxy compounds derived from 5,5-dimethylhydantoin and the like; alicyclic epoxy resins such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and the like; divalent glycidyl ether compounds such as diglycidyl ether compounds and the like derived from dihydric phenols such as N,N-diglycidylaniline and the like, amines or halogenated bisphenols such as tetrabromobisphenol A and the like. Further, the resin composition of the present invention may also contain cyanate resins such as 2,2-bis(4-cyanatephenyl)propane and the like.
- The epoxy resin component of the present invention is obtained by mixing the stilbene-based epoxy compound (A) represented by the general formula (1) with the polyfunctional epoxy compound (B).
- The content of the epoxy compound (A) is, for example, from 1 to 99% by weight, preferably from 20 to 99% by weight, and more preferably from 30 to 90% by weight based on the total amount of the epoxy compound (A) and the epoxy compound (B).
- If only the polyfunctional epoxy compound (B) is used, melt viscosity of the resin is high, therefore, when a filler is used in large amount, flowing property of the whole resin composition in heat-melting becomes low, molding property deteriorates, gloss on the surface of the cured molded article disappears, and sometimes, unfilled portion is formed in the cured material. By combining the stilbene-based epoxy compound (A) with the polyfunctional epoxy compound (B), high filling with a filler which is difficult when the polyfunctional epoxy is used alone can be easily accomplished, and in addition, a cured material having excellent molding property is obtained.
- When the content of the epoxy compound(A) is, for example, from 1 to 60% by weight based on the total amount of the epoxy compound (A) and the epoxy compound(B), flowing property of the whole composition is improved and a molded article having high Barcole harness can be obtained. The content of the epoxy compound(A) is preferably from 20 to 60% by weight, and more preferably from 30 to 60% by weight which are epoxy resin components. When the content is lower than 1% by weight, the softening point becomes lower to make the handling property insufficient.
- The epoxy compound (A) has a low melt viscosity and can contain a large amount of filler without deteriorating flowing property of the whole resin composition, but the epoxy compound (A) alone, sometimes cannot afford a molded article having high Barcole hardness. By combining the polyfunctional epoxy compound (B) with the stilbene-based epoxy compound (A), it becommes possible to increase crosslinking density to make the Barclole hardness high.
- For the above purpose, the content of the polyfunctional epoxy compound (B) is, for example, from 1 to not more than 40% by weight based on the total amount of the epoxy compound(A) and the epoxy compound(B), preferably from 1 to 30% by weight, and more preferably from 10 to 30% by weight. When the content is lower than 1% by weight, the effect of improving Barcole hardness is insufficient.
- The epoxy compound (A) of the present invention has a melt viscosity at 150 DEG C of preferably less than 1 poise, and more preferably less than 0.5 poise. The polyfunctional epoxy compound (B) has a melt viscosity at 150 DEG C of preferably less than 10 poise, and more preferably less than 5 poise.
- In practical use, the epoxy compound (A) and the polyfunctional epoxy resin (B) may be mixed with a filler and the like, or the epoxy components may be previously melted and mixed or may be melted and mixed previously with the resin component (C) such as an epoxy curing agent and the like before use.
- As the epoxy curing agent (C), known curing agents can be used. Examples thereof include polyhydric phenols such as phenol novolak and the like, amine-based curing agents such as dicyanediamide, diaminodiphenylmethane, diaminodiphenylsulfone and the like, acid anhydride curing agents such as pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid, and the like, and in view of moisture resistance, polyhydric phenols are preferable.Further, examples of polyhydric phenols as the epoxy curing agent include polycondensates of one or more phenols such as phenol, various alkylphenols, naphthol and the like with aldehydes such as formaldehyde, acetaldehyde, acrolein, glyoxal, benzaldehyde, naphthaldehyde, hydroxybenzaldehyde and the like or ketones such as cyclohexanone, acetophenone and the like; vinyl polymerization type polyhydric phenols such as polyvinylphenol, polyisopropenylphenol and the like; reaction products of phenols with diols such as a compound represented by the following formula
- Usually, the amount of the curing agent is preferably from 0.7 to 1.2 equivalent based on the epoxy resin. When the amount is less than 0.7 equivalent, or more than 1.2 equivalent, curing is incomplete in either case.
- When the epoxy resin composition of the present invention is cured, known curing accelerators can be used.
- Examples of these accelerators include, but not limited to, organic phosphine compounds such as triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cycnoethylphosphine and the like and tetraphenyl borate salts thereof; tert-amines such as tributylamine, triethylamine, 1,8-diazabicyclo(5,4,0)undecene-7, triamylamine and the like; quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammoniumtetraphenyl borate and the like; imidazoles, and the like. Among them, organic phosphine compounds, 1,8-diazabicyclo(5,4,0)undecene-7, and imidazoles are preferred in view of moisture resistance and curing property, and triphenylphosphine is particularly preferred.
- Examples of the inorganic filler (D) in the epoxy resin composition of the present invention include silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass, fiber and the like, and in particular, silica and alumima are preferred. These fillers having different form (spherical or crushed type) or different size may also be mixed to increase filling amount for use.
- In view of moisture resistance and molding property, the compounding ratio of the inorganic filler is from 25 to 95% by weight based on the total amount of the resin composition, preferably from 50 to 95% by weight, more preferably from 70 to 95% by weight, and more preferably from 80 to 92% by weight.
- In the case of using a spherical powder as the inorganic filler, the form may advantageously be substantial sphere containing no sharp angle and having an aspect ratio of 1.0 to 1.2. A sphere having sphericity near that of a commercially available spherical silica powder produced by a spray coating method or sol-gel method is preferred, and a sphere having sphericity more close to that of a real sphere is more preferable. When sphering treatment is difficult, the inorganic material is processed into a fine powder, and then formed to a spherical powder by a mechanochamichal method with adding a binder to the powder.
- The form of the crushed powder may be heteromorphic body such as a polyhedron having angle and the like. Among other, amorphous or crystalline quarts crushed powders obtained by grinding a synthetic or natural quarts lump is suitable, and specifically, fused crushed-silica and the like are suitable.
- As the spherical powder used in the present invention, any powder can be used, and as one example, which composed of three groups, namely, x, y and z components, will be described. The x, y and z components have an average particle size from 0.1 to 1.5 mu m, an average particle size from 2 to 15 mu m and an average particle size from 20 to 70 mu m respectively, and more preferably an average particle size from 0.1 to 1.0 mu m, an average particle size from 2 to 10 mu m and an average particle size from 20 to 50 mu m respectively. When a powder having an average particle size of less than 0.1 mu m is used, due to flocculation of the powder each other, sometimes uniform dispersion in the resin composition becomes difficult and flowing property is lost, and the powder having an average particle size of over 70 mu m can not easily filled in fine part of a semiconductor element.When respective average particle sizes of the x, y and z components are out of the above-described ranges, flowing property of the resin composition lowers. It is preferable that the particle size distribution of each spherical powder used in the present invention is narrower, and further, a powder of monodistribution system is preferred. Therefore, it is preferable to use a powder in which x, y and z components are treated for uniforming respective particle sizes by sieving operation. The average particle size is defined as a 50 % diameter of cumulative particle distribution measured by using an apparatus such as a laser scattering particle size distribution measuring apparatus and the like.
- Regarding the compounding ratio of the spherical powders x, y and z, ratios by volume of the x, y and z components based on the calculated total volume of the x, y and z components may be advantageously from 10 to 24% by volume, from 0.1 to 66% by volume and from 24 to 76% by volume respectively, and more advantageously from 10 to 24% by volume, from 0.1 to 36% by volume and from 57 to 76% by volume respectively, and more preferably from 10 to 20% by volume, from 4 to 30% by volume and from 60 to 76% by volume respectively. When the ratios are out of these ranges, flowing property of the resin composition lowers.
- The aforesaid descriptions of % by weight in the present invention are obtained by calculation using values obtained by dividing respective weights of the w, y and z components by respective true specific gravity, as volumes of respective components. In general, the apparent volume of a particle having particle size distribution changes depending on manner for filling into a measuring vessel, and when aggregates of heterogeneous particles are mixed, the apparent volumes before and after the mixing are different. Therefore, in the above-described description, apparent volume is not used in calculation of % by volume of each component of the particle aggregate.
- The crushed powder (m component) used in the present invention has an average particle size of 1 to 70 mu m, preferably 1 to 30 mu m. Regarding the compounding ratio of the crushed powder (m component), the ratio by weight of them component based on the total weight of the spherical powder component and the crushed powder m component is preferably from 1 to 30% by weight. When the compounding ratio is lower than this range, effect for decreasing fin or flash (a resin thin film due to flowing out of a resin component) generated depending on kind of the resin, and forms of an encapsulating apparatus and mold is poor, and when over this range, flowing property of the resin composition decreases.
- The epoxy resin composition according to the invention contains a pyrogenically produced silica, which has been surface modified with Hexamethyldisilazane (HMDS) and structurally modified by a ball mill.
- This pyrogenically produced silica is known from the
US 5,959,005 . - In a preferred subject of the invention the pyrogenically produced, hydrophobized and structurally modified silica can be the AEROSIL R8200, which has the following physical-chemical datas:
Properties Unit Typical Value Specific surface area (BET) m2/g 160 ± 25 Carbon content wt. % 2.0 - 4.0 Tapped density* (approx. value) acc. to DIN EN ISO 787/11, Aug. 1983 g/l approx. 140 Moisture* 2 hours at 105 °C wt. % ≤ 0.5 pH-value in 4 % dispersion ≥ 5.0 SiO2-content based on ignited material wt. % ≥ 99.8 * ex plant
The data represents typical values and not production parametersRegistration CAS-No. 68909-20-6 EINECS 272-697-1 TSCA (USA), AICS (Australia), Registered CEPA (Canada), PICCS (Philippines) MITI (Japan) 1-548/7-476 ECL (Korea) KE-34696 NEPA (China) List III - It is preferable that the fillers used in the present invention is previously mixed sufficiently. Specifically, the mixing can be conducted by using an apparatus such as a mixer, cokneader and the like utilizing a rotating blade or air, an apparatus which vibrates, shakes or rotates a vessel, and the like. For judging whether the fillers are fully kneaded or not, it may be advantageous that particle size distributions of samples in different places are measured, and whether they are substantially the same or not is checked. Further, optionally, the filler may be previously treated with a coupling agent or a resin, for use. As the treatment method, there are a method in which mixing is conducted using a solvent, then the solvent is distilled off, and a method in which the coupling agent or the resin is directly mixed with the filler, and the mixture is treated using a mixed.
- In the epoxy resin composition of the present invention, in addition, a mold-releasing agent such as natural wax, synthetic wax, higher fatty acid and metal salt thereof, or paraffin and the like, or a coloring agent such as carbon black, and further, a surface treating agent such as a silane coupling agent and the like, may be optionally added. Further, a flame retardant such as antimony trioxide, phosphorus compound, brominated epoxy resin and the like may be added. For exhibiting flame retardant effect, a brominated epoxy resin is particularly preferable.
- Further, for lowering stress, various elastomers may be added or previously reacted for use. Examples thereof include addition type or reaction type elastomers and the like such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber, silicone oil and the like.
- For encapsulating electronic parts such as a semiconductor and the like and producing a resin encapsulated semiconductor device using the epoxy resin composition of the present invention, curing-molding may advantageously be effected by a conventionally known molding method such as transfer mold, compression mold, injection mold and the like.
- The epoxy resin according to our invention shows the following advantages:
- Low moisture absorption in comparison to hydrophilic fillers
- High possible loading levels
- Improved storage stability
- Improved application properties
Claims (6)
- An epoxy resin composition comprising:(A) an epoxy compound represented by the general formula (1):(B) a polyfunctional epoxy compound having a functional group number of two or more, and(C) an epoxy curing agent containing a phenolic hydroxyl group,wherein the proportion of the epoxy compound (A) is from 0.1 to 99% by weight based on the total weight of the epoxy compounds (A) and (B), whereas the epoxy resin composition contains a pyrogenically produced silica, which has been surface modified with Hexamethyldisilazane (HMDS) and structurally modified by a ball mill.
- The epoxy resin composition according to claim 1, wherein the proportion of the epoxy compound (A) is from 20 to 99% by weight based on the total weight of the epoxy compounds (A) and (B).
- The epoxy resin composition according to claim 1, which further comprises an inorganic filler (D) in an amount of from 25 to 95% by weight based on the weight of the whole resin composition.
- The epoxy resin composition according to claim 3, wherein the inorganic filler (D) is in an amount of from 50 to 95% by weight based on the weight of the whole resin composition.
- The epoxy resin composition according to claim 1 or 2, wherein the polyfunctional epoxy compound (B) is a glycidyl ether compound of phenol novolaks or a glycidyl ether compound of trisphenolmethane novolaks.
- A resin-encapsulated semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition of claim 1 or 3.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602008006681T DE602008006681D1 (en) | 2008-05-15 | 2008-05-15 | Electronic packaging |
AT08156292T ATE508154T1 (en) | 2008-05-15 | 2008-05-15 | ELECTRONIC PACKAGING |
PL08156292T PL2119737T3 (en) | 2008-05-15 | 2008-05-15 | Electronic packaging |
EP08156292A EP2119737B1 (en) | 2008-05-15 | 2008-05-15 | Electronic packaging |
ES08156292T ES2364790T3 (en) | 2008-05-15 | 2008-05-15 | ELECTRONIC WRAPPING |
PCT/EP2009/054393 WO2009138301A1 (en) | 2008-05-15 | 2009-04-14 | Electronic packaging |
CN2009801174440A CN102027036A (en) | 2008-05-15 | 2009-04-14 | Electronic packaging |
KR1020107025422A KR20110017853A (en) | 2008-05-15 | 2009-04-14 | Electronic packaging |
JP2011508855A JP2011521033A (en) | 2008-05-15 | 2009-04-14 | Electronic packaging |
US12/992,684 US20110163461A1 (en) | 2008-05-15 | 2009-04-14 | Electronic packaging |
TW098115688A TW201004995A (en) | 2008-05-15 | 2009-05-12 | Electronic packaging |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08156292A EP2119737B1 (en) | 2008-05-15 | 2008-05-15 | Electronic packaging |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2119737A1 EP2119737A1 (en) | 2009-11-18 |
EP2119737B1 true EP2119737B1 (en) | 2011-05-04 |
Family
ID=39738214
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08156292A Not-in-force EP2119737B1 (en) | 2008-05-15 | 2008-05-15 | Electronic packaging |
Country Status (11)
Country | Link |
---|---|
US (1) | US20110163461A1 (en) |
EP (1) | EP2119737B1 (en) |
JP (1) | JP2011521033A (en) |
KR (1) | KR20110017853A (en) |
CN (1) | CN102027036A (en) |
AT (1) | ATE508154T1 (en) |
DE (1) | DE602008006681D1 (en) |
ES (1) | ES2364790T3 (en) |
PL (1) | PL2119737T3 (en) |
TW (1) | TW201004995A (en) |
WO (1) | WO2009138301A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102081876B1 (en) * | 2011-08-31 | 2020-02-26 | 히타치가세이가부시끼가이샤 | Resin composition, resin sheet, resin sheet with metal foil, hardened resin sheet, structure, and semiconductor device for power or light source |
KR101321981B1 (en) * | 2012-10-25 | 2013-10-28 | 한국전기연구원 | Manufacturing method of solvent content controllable silica-epoxy hybrid packaging materials |
KR101985255B1 (en) * | 2012-11-30 | 2019-06-03 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board comprising isolation using the same |
US9462689B2 (en) | 2012-11-30 | 2016-10-04 | Lg Innotek Co., Ltd. | Epoxy resin composition and printed circuit board including insulating layer using the epoxy resin composition |
KR101985256B1 (en) * | 2012-11-30 | 2019-06-03 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board comprising isolation using the same |
KR101984791B1 (en) * | 2012-12-12 | 2019-09-03 | 엘지이노텍 주식회사 | Epoxy resin composite, prepreg and printed circuit board using the same |
KR101973685B1 (en) | 2012-12-12 | 2019-08-26 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
KR102012311B1 (en) * | 2012-12-12 | 2019-08-20 | 엘지이노텍 주식회사 | Resin composite and printed circuit board using the same |
KR101973686B1 (en) * | 2012-12-12 | 2019-08-26 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
KR101952356B1 (en) * | 2012-12-14 | 2019-02-26 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
KR102034228B1 (en) * | 2012-12-14 | 2019-10-18 | 엘지이노텍 주식회사 | Epoxy resin composite, prepreg and printed circuit board using the same |
KR102022430B1 (en) * | 2013-05-28 | 2019-09-18 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board comprising isolation using the same |
KR20150097359A (en) | 2014-02-18 | 2015-08-26 | 주식회사 엘지화학 | Encapsulation film and organic electronic device comprising the same |
Family Cites Families (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3333776A (en) * | 1965-04-05 | 1967-08-01 | Dow Corning | Hydrophobic silica as a grinding aid |
US4043969A (en) * | 1973-04-23 | 1977-08-23 | National Semiconductor Corporation | Casting compound for semiconductor devices |
JPS6031517A (en) | 1983-07-29 | 1985-02-18 | Sumitomo Chem Co Ltd | Production of epoxy resin |
JP2501804B2 (en) * | 1986-11-20 | 1996-05-29 | 松下電工株式会社 | Epoxy resin composition |
EP0289632A1 (en) * | 1987-05-04 | 1988-11-09 | American Cyanamid Company | High green strength induction curable adhesives |
JPH01297453A (en) * | 1988-05-24 | 1989-11-30 | Matsushita Electric Works Ltd | One-pack epoxy resin composition |
DE4119332A1 (en) * | 1991-06-12 | 1992-12-17 | Huels Chemische Werke Ag | METHOD FOR PRODUCING METHYLIDE GROUPS (ALPHA), (OMEGA) -UNSATURED OLIGOMERS FROM (ALPHA), (OMEGA) -DIOLEFINES IN THE PRESENCE OF ALUMINUM ORGANIC COMPOUNDS AS A CATALYST |
DE4233021A1 (en) * | 1992-10-01 | 1994-04-07 | Huels Chemische Werke Ag | Organosilane polycondensates |
US6193795B1 (en) * | 1993-08-02 | 2001-02-27 | Degussa Corporation | Low structure pyrogenic hydrophilic and hydrophobic metallic oxides, production and use |
DE19508088A1 (en) * | 1995-03-08 | 1996-09-12 | Huels Chemische Werke Ag | Process for the preparation of an oligomer mixture from alpha, omega-diolefins |
JP3508289B2 (en) * | 1995-05-02 | 2004-03-22 | 住友化学工業株式会社 | Epoxy resin composition and resin encapsulated semiconductor device |
EP0739877B1 (en) * | 1995-04-27 | 1999-08-04 | Sumitomo Chemical Company Limited | Epoxy resin, resin composition, and resin-encapsulated semiconductor device |
DE19616781A1 (en) * | 1996-04-26 | 1997-11-06 | Degussa | Silanized silica |
US5959005A (en) | 1996-04-26 | 1999-09-28 | Degussa-Huls Aktiengesellschaft | Silanized silica |
DE19624032A1 (en) * | 1996-06-17 | 1997-12-18 | Huels Chemische Werke Ag | Oligomer mixture of condensed alkylalkoxysilanes |
DE19639782A1 (en) * | 1996-09-27 | 1998-04-02 | Huels Chemische Werke Ag | Glycidether, acrylic and / or methacrylic functional organopolysiloxane-containing compositions based on water, processes for their preparation and their use |
JPH10298170A (en) * | 1997-02-28 | 1998-11-10 | Sumitomo Chem Co Ltd | Epoxy compound, its production, its purification, epoxy resin composition and resin-sealed semiconductor device |
TW593528B (en) * | 1997-03-31 | 2004-06-21 | Sumitomo Chemical Co | Epoxy resin composition |
DE19818924A1 (en) * | 1998-04-28 | 1999-11-04 | Degussa | Surface-modified fillers, processes for their production and their use |
JP2000044773A (en) * | 1998-07-28 | 2000-02-15 | Konishi Co Ltd | One pack moisture-curable composition |
DE19834990B4 (en) * | 1998-08-03 | 2005-09-15 | Degussa Ag | Acryloxypropyl or methacryloxypropyl-containing siloxane oligomers, processes for their preparation and their use |
DE19848351A1 (en) * | 1998-10-21 | 2000-04-27 | Degussa | Camera with internal exposure function has controller that determines light output of light output device according to sensitivity of film determined by film sensitivity detector |
DE19849308A1 (en) * | 1998-10-27 | 2000-05-04 | Degussa | Aminopropyl functional siloxane oligomers |
DE19904132C2 (en) * | 1999-02-03 | 2002-11-28 | Degussa | Composition of fluoroorganofunctional silanes and siloxanes, process for their preparation and their use |
DE19929021A1 (en) * | 1999-06-25 | 2000-12-28 | Degussa | Functional organylorganyloxysilanes on carriers in cable compounds |
DE19961972A1 (en) * | 1999-12-22 | 2001-06-28 | Degussa | Organosilane and / or organosiloxane-containing agent for filled polyamide |
EP1195416A3 (en) * | 2000-10-05 | 2005-12-28 | Degussa AG | Polymerisable silicone-organic nanocapsules |
EP1195417B1 (en) * | 2000-10-05 | 2009-10-14 | Evonik Degussa GmbH | Silicone-organic nanocapsules |
DE10056344A1 (en) * | 2000-11-14 | 2002-05-16 | Degussa | n-Propylethoxysiloxanes, process for their preparation and their use |
DE10100384A1 (en) * | 2001-01-05 | 2002-07-11 | Degussa | Process for modifying the functionality of organofunctional substrate surfaces |
EP1249470A3 (en) * | 2001-03-30 | 2005-12-28 | Degussa AG | Highly filled pasty siliconorganic nano and/or microhybridcapsules containing composition for scratch and/or abrasion resistant coatings |
ATE366279T1 (en) * | 2001-03-30 | 2007-07-15 | Degussa | ORGANIC SILICON NANO-MICROHYBRID SYSTEMS OR MICROHYBRID SYSTEMS CONTAINING COMPOSITION FOR SCRATCH AND ABRASION RESISTANT COATINGS |
DE10132942A1 (en) * | 2001-07-06 | 2003-01-23 | Degussa | Siloxane oligomers, process for their preparation and their use |
DE10141687A1 (en) * | 2001-08-25 | 2003-03-06 | Degussa | Agent for coating surfaces containing silicon compounds |
DE10142555A1 (en) * | 2001-08-30 | 2003-03-20 | Degussa | Means for improving the scorch conditions in the production of grafted and / or crosslinked polymers and filled plastics |
DE10159952A1 (en) * | 2001-12-06 | 2003-06-18 | Degussa | Use of liquid or unsaturated organosilane / mixtures applied on carrier material for the production of moisture-crosslinked and filled cable compounds |
DE10212523A1 (en) * | 2002-03-21 | 2003-10-02 | Degussa | Air-drying, silane-containing coating agents |
DE10238369A1 (en) * | 2002-08-22 | 2004-03-04 | Degussa Ag | Agent as an adhesion promoter for filled and peroxidically cross-linked rubber compounds |
DE10327624B3 (en) * | 2003-06-20 | 2004-12-30 | Degussa Ag | Organosilicon compounds, process for their preparation, and their use |
DE10362060B4 (en) * | 2003-10-21 | 2009-07-09 | Altana Coatings & Sealants Gmbh | Packaging material with a barrier layer for gases |
DE102004007456A1 (en) * | 2004-02-13 | 2005-09-01 | Degussa Ag | Highly filled polyolefin compounds |
KR100846547B1 (en) * | 2004-07-13 | 2008-07-15 | 히다치 가세고교 가부시끼가이샤 | Epoxy resin molding material for sealing and electronic component device |
JP4977973B2 (en) * | 2004-07-13 | 2012-07-18 | 日立化成工業株式会社 | Epoxy resin molding material for sealing and electronic component device |
DE102004037043A1 (en) * | 2004-07-29 | 2006-03-23 | Degussa Ag | Block condensates of organofunctional siloxanes, their preparation, use and their properties |
DE102004049427A1 (en) * | 2004-10-08 | 2006-04-13 | Degussa Ag | Polyether-functional siloxanes, polyethersiloxane-containing compositions, processes for their preparation and their use |
DE102005004872A1 (en) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Aqueous emulsions of functional alkoxysilanes and their condensed oligomers, their preparation and use for surface treatment |
DE102005004871A1 (en) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Highly viscous aqueous emulsions of functional alkoxysilanes, their condensed oligomers, organopolysiloxanes, their preparation and their use for the surface treatment of inorganic materials |
DE102006013090A1 (en) * | 2006-03-20 | 2007-09-27 | Georg-August-Universität Göttingen | Composite material made of wood and thermoplastic material |
DE102006033310A1 (en) * | 2006-07-17 | 2008-01-31 | Evonik Degussa Gmbh | Mixtures of silicon-containing coupling reagents |
PL1982964T3 (en) * | 2007-04-20 | 2019-08-30 | Evonik Degussa Gmbh | Preparation containing organosilicium compound and its use |
DE102007038314A1 (en) * | 2007-08-14 | 2009-04-16 | Evonik Degussa Gmbh | Process for the controlled hydrolysis and condensation of epoxy-functional organosilanes and their condensation with further organofunctional alkoxysilanes |
DE102007045186A1 (en) * | 2007-09-21 | 2009-04-09 | Continental Teves Ag & Co. Ohg | Residue-free, layer-forming, aqueous sealing system for metallic silane-based surfaces |
DE102008001808A1 (en) * | 2008-05-15 | 2009-11-19 | Evonik Degussa Gmbh | coating composition |
DE102008001855A1 (en) * | 2008-05-19 | 2009-11-26 | Evonik Degussa Gmbh | Two-component composition for the production of flexible polyurethane gelcoats |
-
2008
- 2008-05-15 ES ES08156292T patent/ES2364790T3/en active Active
- 2008-05-15 DE DE602008006681T patent/DE602008006681D1/en active Active
- 2008-05-15 EP EP08156292A patent/EP2119737B1/en not_active Not-in-force
- 2008-05-15 AT AT08156292T patent/ATE508154T1/en not_active IP Right Cessation
- 2008-05-15 PL PL08156292T patent/PL2119737T3/en unknown
-
2009
- 2009-04-14 JP JP2011508855A patent/JP2011521033A/en active Pending
- 2009-04-14 WO PCT/EP2009/054393 patent/WO2009138301A1/en active Application Filing
- 2009-04-14 CN CN2009801174440A patent/CN102027036A/en active Pending
- 2009-04-14 US US12/992,684 patent/US20110163461A1/en not_active Abandoned
- 2009-04-14 KR KR1020107025422A patent/KR20110017853A/en not_active Application Discontinuation
- 2009-05-12 TW TW098115688A patent/TW201004995A/en unknown
Also Published As
Publication number | Publication date |
---|---|
TW201004995A (en) | 2010-02-01 |
CN102027036A (en) | 2011-04-20 |
DE602008006681D1 (en) | 2011-06-16 |
WO2009138301A1 (en) | 2009-11-19 |
US20110163461A1 (en) | 2011-07-07 |
KR20110017853A (en) | 2011-02-22 |
EP2119737A1 (en) | 2009-11-18 |
PL2119737T3 (en) | 2011-09-30 |
ES2364790T3 (en) | 2011-09-14 |
JP2011521033A (en) | 2011-07-21 |
ATE508154T1 (en) | 2011-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2119737B1 (en) | Electronic packaging | |
JP2007262398A (en) | Epoxy resin composition and electronic part device | |
WO2011114935A1 (en) | Epoxy resin composition and cured substance | |
CN1203104C (en) | Epoxy resin composition for semiconductor encapsulation | |
KR100539729B1 (en) | Epoxy Resin Compositions and Resin-Enclosed Semiconductor Devices | |
JP4264769B2 (en) | Epoxy resin composition and semiconductor sealing material | |
JP5167587B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
JP3413962B2 (en) | Epoxy resin composition for molding | |
JP3508289B2 (en) | Epoxy resin composition and resin encapsulated semiconductor device | |
JP2001240726A (en) | Epoxy resin composition and semiconductor device | |
JP2004339371A (en) | Epoxy resin composition and cured product thereof | |
JP2001151863A (en) | Epoxy resin composition for semiconductor sealing use | |
JPH0733429B2 (en) | Epoxy resin composition | |
JP6655359B2 (en) | Method for producing electronic / electric parts and epoxy resin composition | |
JP2001247652A (en) | Epoxy resin composition and semiconductor device | |
JP5177480B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
JPH08134329A (en) | Production of epoxy resin composition | |
JP5435978B2 (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
JP2010275479A (en) | Epoxy resin composition for sealing semiconductor and semiconductor device | |
JPH10330458A (en) | Epoxy resin composition and resin-sealed type semiconductor device | |
JP2001270931A (en) | Epoxy resin composition and semiconductor device | |
JP2004155841A (en) | Sealing resin composition, and semiconductor sealing device | |
JP2003026764A (en) | Epoxy resin composition for semiconductor sealing and semiconductor device | |
JPH09309941A (en) | Epoxy resin composition and resin-sealed semiconductor device | |
JPH10330457A (en) | Epoxy resin composition and resin-sealed type semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
17P | Request for examination filed |
Effective date: 20100421 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
17Q | First examination report despatched |
Effective date: 20100927 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602008006681 Country of ref document: DE Date of ref document: 20110616 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602008006681 Country of ref document: DE Effective date: 20110616 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2364790 Country of ref document: ES Kind code of ref document: T3 Effective date: 20110914 |
|
REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110804 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110905 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110805 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110904 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20120207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110515 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111123 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602008006681 Country of ref document: DE Effective date: 20120207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110515 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110804 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110504 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20140521 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20140527 Year of fee payment: 7 Ref country code: IT Payment date: 20140523 Year of fee payment: 7 Ref country code: CH Payment date: 20140521 Year of fee payment: 7 Ref country code: DE Payment date: 20140521 Year of fee payment: 7 Ref country code: NL Payment date: 20140521 Year of fee payment: 7 Ref country code: ES Payment date: 20140528 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20140428 Year of fee payment: 7 Ref country code: BE Payment date: 20140523 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602008006681 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150515 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150531 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150515 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150531 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20150601 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150601 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150515 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150601 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20160628 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150516 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150515 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150531 |